Polyisocyanurate compositions and composites

ABSTRACT

Polyisocyanurate systems, pultrusion of those systems to produce reinforced polyisocyanurate matrix composites, and to composites produced thereby. The polyisocyanurate systems include a polyol component, an optional chain extender, and an isocyanate. The polyisocyanurate systems have extended initiation times of about 5 minutes to about 30 minutes at room temperature, and can be snap cured.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of U.S. patent applicationSer. No. 09/858,377, filed on May 16, 2001, which is a continuation ofinternational application number PCT US99/26854, filed on Nov. 12, 1999,and further claims priority to U.S. Provisional Application No.60/108611, file Nov. 16, 1998.

TECHNICAL FIELD

[0002] The invention relates to polyisocyanurate systems, fiberreinforced polyisocyanurate matrix composites, and manufacture of thosecomposites by pultrusion.

BACKGROUND ART

[0003] Pultrusion is a highly cost effective method for making fiberreinforced, resin matrix composites. The primary raw materials used inpultrusion are resin and reinforcement. Fillers and additives such ascalcium carbonate, clay, mica, pigments, UV stabilizers can be added tothe resin to enhance the physical, chemical and mechanical properties ofthe pultruded product.

[0004] Pultrusion is typically done by the injection die or open bathprocess. The open bath process is the most common. The injection dieprocess, however, is gaining importance due to environmental concernsabout the large amounts of volatile contaminants released in the openbath process.

[0005] In a typical open bath process, reinforcement material in theform of fibers, mat or roving is pulled continuously through an openbath of resin to produce an impregnated reinforcement. The impregnatedreinforcement is pulled through form plates to remove excess resin, andthen through a curing die to cure the resin and yield a finishedproduct.

[0006] In the injection die pultrusion process, reinforcement materialis passed through a closed injection die that has resin injection ports.The resin is injected under pressure through the ports to impregnate thereinforcement material. The impregnated reinforcement is pulled throughthe injection die to produce a shaped product.

[0007] Resins which have been used in the open bath and injection diemethods of pultrusion include thermoset resins such as unsaturatedpolyester, epoxy, phenolics, methacrylates and the like, as well asthermoplastic resins such as PPS, ABS, Nylon 6. Blocked polyurethaneprepolymers also have been used. Polyester and epoxy resins aregenerally slower reacting than polyisocyanurates. In addition, the useof blocked polyurethane resins in pultrusion has the disadvantage ofdeblocking of the isocyanate, which creates environmental concerns.

[0008] A need therefore exists for resins such as polyisocyanurate andpolyurethane resins which may be used in pultrusion, especiallyinjection die pultrusion, without these disadvantages.

DISCLOSURE OF THE INVENTION

[0009] The invention relates to polyisocyanurate systems, preferablymiscible polyisocyanurate systems, having an isocyanate component and apolyol component. The polyol component includes any of polyester polyolsand polyether polyols. One or more polyester polyols may be blended withone or more polyether polyols in any ratio for use in the polyolcomponent.

[0010] The polyether polyols have a functionality of about 2 to about 6and a molecular weight of about 300-6000. The polyol component alsoincludes a catalyst capable of initiating both a urethane and anisocyanurate reaction. The isocyanate can be an isocyanate prepolymer.The isocyanate and the polyol component can be present in a ratio ofabout 0.3 to about 9.0 in an amount sufficient to yield an index ofabout 200 to about 900.

[0011] The polyol component also can include a chain extender such asglycerols and diols having at least about 2 hydroxyl groups and amolecular weight less than about 300. When a chain extender is present,the polyol may be present in an amount of up to about 1-99% and thechain extender may be may be present in an amount of up to about 1-99%based on total weight of the polyol component.

[0012] A preferred polyisocyanurate system includes an isocyanatecomponent and a polyether polyol component where the polyether polyol ispolyethylene oxide capped polypropylene oxide polyether polyol havingethylene oxide content of about 21%, a functionality of 2, and ahydroxyl value of 30 mg KOH/gm, the chain extender is dipropyleneglycol, and the isocyanate is a mixture of 2,4′MDI, 4,4′MDI and pMDIhaving about 19.5% 2,4′-MDI, 60.9% 4,4′-MDI, about 19.6% p-MDI, and anNCO value of 32.5. The polyisocyanurate systems, at an index of fromabout 300 to about 700 fully cure at 120-140 C with an isocyanateconversion of about 90%. Another preferred polyisocyanurate systemincludes an isocyanate component and a polyether polyol component wherethe polyether polyol is PPG425 and the isocyanate is a mixture of2,4′MDI, 4,4′MDI and pMDI having about 19.5% 2,4′-MDI, 60.9% 4,4′-MDI,about 19.6% p-MDI, and an NCO value of 32.5.

[0013] The invention also relates to a pultrusion process for preparinga cured polyisocyanurate fiber reinforced polymer composite. The processentails pulling continuous fibers through an impregnation die, supplyinga polyol component having a catalyst capable of initiating both aurethane reaction and a isocyanurate reaction, and an isocyanatecomponent to a static mixer to produce a polyisocyanurate reactionmixture and feeding the reaction mixture to the impregnation die,contacting the fibers with the precursor mixture in the impregnationchamber for a time period and at a temperature sufficient to causesubstantial polymerization of the reaction mixture within theimpregnation chamber to produce a composite of fibers coated by thepolyisocyanurate reaction mixture, directing the composite of coatedfibers through a heated curing die to at least partially cure thepolyisocyanurate reaction mixture to produce a solid fiber reinforcedpolyisocyanurate matrix composite, and drawing the cured composite fromthe die. The temperature in the impregnation chamber is less than thetemperature required to initiate a polyisocyanurate reaction. The fibersare at ambient temperature before they enter the impregnation die. Thefibers and the reaction mixture are supplied concurrently to theimpregnation die. During pultrusion, the polyisocyanurate reactionmixture may be present in the injection die for less than about 50seconds.

[0014] The polyisocyanurate systems of the invention are two componentsystems. Mixing of the two components can be achieved by using a staticor dynamic mixer. A static mixer is preferred. Type I and Type IImiscible two component polyisocyanurate systems are preferred.

[0015] Having summarized the invention, the invention will now bedescribed in detail by reference to the following disclosure andnon-limiting examples.

MODES FOR CARRYING OUT THE INVENTION

[0016] Glossary: The following names and abbreviations are understood tohave the meanings defined below:

[0017] 1. 1,4 BD is 1,4 butane diol;

[0018] 2. 1,3 BD is 1,3 butane diol;

[0019] 3. 2,3 BD is 2,3 butane diol;

[0020] 4. 1,2 PD is 1,2 propane diol;

[0021] 5. 2m 1,3 PD is 2-methyl-1,3-propane diol;

[0022] 6. BiCat 8 is Bismuth-Zinc Neodeconate from Shepherd ChemicalCo.;

[0023] 7. Dabco DC 1027 is 30% triethylenediamine (TEDA) in Ethylene.Dabco 33LV is TEDA in DPG from Air Products and Chemicals, Allentown,Pa.

[0024] 8. Dabco K15 is a catalyst of a potassium salt in a glycol fromAir Products and Chemicals, Allentown, Pa.;

[0025] 9. Dabco T-12 is 100% dibutyl tin dilaurate from Air Products andChemicals, Allentown, Pa.;

[0026] 10. Dabco T-45 is a potassium carboxylate catalyst from AirProducts and Chemicals, Allentown, Pa.;

[0027] 11. Dabco TMR is a tetra alkylammonium 2-ethylhexonate dissolvedin DPG, from Air Products.;

[0028] 12. Fomrez UL-29 is a mixture of octylmercapto acetate in apolyol carrier available from Witco Corporation, Greenwich, Conn.;

[0029] 13. DEG is diethylene glycol;

[0030] 14. DPG is dipropylene glycol;

[0031] 15. Glycerin is 99.5% pure trihydroxy alcohol from QuakerChemical Co.;

[0032] 16. Isocyanate A is polymeric MDI having an MDI content of about44 wt. % and an NCO value of about 30.7 from Huntsman Polyurethanes;

[0033] 17. Isocyanate B is uretonimine modified 4,4′MDI having an NCOvalue of 29 from Huntsman Polyurethanes;

[0034] 18. Isocyanate C is a mixture of 2,4′MDI,4,4′MDI and pMDI havingabout 9.4% 2,4′-MDI, 60.9% 4,4′-MDI, about 29.7% p-MDI, and an NCO valueof 32.1 from Huntsman Polyurethanes.

[0035] 19. Isocyanate D is a mixture of 2,4′MDI,4,4′MDI and pMDI havingabout 19.5% 2,4′-MDI, 60.9% 4,4′-MDI, about 19.6% p-MDI, and an NCOvalue of 32.5 from Huntsman Polyurethanes.

[0036] 20. Isocyanate E is a softblock MDI prepolymer formed from an EOcapped polyoxypropylene diol having a molecular weight of 3740 and EOcap level of 27.1%, remainder polypropylene oxide, and which is 39.7 wt.% of the total prepolymer, 6% of the total prepolymer is a uretoniminecarbodiimide modified pure 4,4′ MDI having an NCO content of 29.3%, andthe remainder of the prepolymer is a mixture of 4,4′ and 2,4′ MDI inwhich the 2,4 MDI is about 2.2-2.8% of the mixed isomer stream, thesoftblock prepolymer having an NCO of 18.9-19.3 and a viscosity at 25 Cof 300-375 cps from Huntsman Polyurethanes.

[0037] 21. Kemester 5721 from Witco Corporation, Greenwich, Conn. istridecyl stearate.

[0038] 22. LC-5615 is nickel acetylacetonate from OSI Specialties;

[0039] 23. LHT 240 is a polyether polyol from Arco Chemical Co.

[0040] 24. Loxiol G71S is the reaction product of adipic acid,pentaerythritol, and oleic acid, having an acid number less than 15 andan hydroxyl number less than 15 from Henkel Corp., Kankakee, Ill.;

[0041] 25. LuWax OP is a solid montanic ester wax from BASF Corp.

[0042] 26. MDI is diphenylmethane diisocyanate;

[0043] 27. MEG is monoethylene glycol;

[0044] 28. Munch 7027/A is a fatty acid ester derivative internal moldrelease agent from Munch Co, Germany;

[0045] 29. Munch 7016 is a fatty acid ester derivative internal moldrelease agent from Munch Co, Germany;

[0046] 30. Munch 0669/1BB is a fatty acid ester derivative internal moldrelease agent from Munch Co, Germany;

[0047] 31. Niax L 5440 is a silicone surfactant that includespolyalkylenoxidimethyl siloxane copolymer available from Union Carbide,Sisterville, W.V.

[0048] 32. Polymeric MDI is defined as a blend of 2,2′ MDI, 2,4′ MDI,and 4,4′ MDI diisocyanates, where 4,4′ MDI is the predominate isomer,the remainder being isocyanates having a functionality greater than 3.The weight ratio of diisocyanates to higher functionality isocyanatesvaries from 70:30 to 30:70.

[0049] 33. Polyol A is polyethylene oxide capped polypropylene oxidepolyether polyol having ethylene oxide content of about 21%, afunctionality of 2, and a hydroxyl value of 30 mg KOH/gm from HuntsmanPolyurethanes;

[0050] 34. Polyol B is polyethylene oxide capped polypropylene oxidepolyether polyol having ethylene oxide content of about 27%, afunctionality of 2, and a hydroxyl value of 30 mg KOH/gm from HuntsmanPolyurethanes;

[0051] 35. Polyol C is polyethylene oxide capped polypropylene oxidepolyether polyol having ethylene oxide content of about 50%, afunctionality of 2, and a hydroxyl value of 30 mg KOH/gm from HuntsmanPolyurethanes;

[0052] 36. Polyol D is a glycerol based polyethylene oxide cappedpolypropylene oxide polyether polyol having an ethylene oxide content ofabout 10%, a functionality of 3, and a hydroxyl value of 56 mg KOH/gmfrom Huntsman Polyurethanes;

[0053] 37. Polyol E is a glycerol based polyethylene oxide cappedpolypropylene oxide polyether polyol having an ethylene oxide content ofabout 17%, a functionality of 3, and a hydroxyl value of 35 mg KOH/gmfrom Huntsman Polyurethanes;

[0054] 38. Polyol F is a glycerol based polypropylene oxide polyetherpolyol having a functionality of 3 and a hydroxyl value of 28 mg KOH/gmfrom Huntsman Polyurethanes;

[0055] 39. Polyol G from Huntsman Polyurethanes is an ethyleneglycol/diethylene glycol initiated adipate polyester polyol having anaverage molecular weight (g/mol) of 2000, a functionality of 2.0, and ahydroxyl number of 55 mg KOH/gm.

[0056] 40. Polyol H from Huntsman Polyurethanes is an ethyleneglycol/butane diol initiated adipate polyester polyol having an averagemolecular weight (g/mol) of 2000, a functionality of 2.0, and a hydroxylnumber of 55 mg KOH/gm.

[0057] 41. Polyol X from Huntsman Polyurethanes has an average molecularweight (g/mole) of 260. Polyol X is a polyether diol that has afunctionality of 3 and a hydroxyl number of 650 mg KOH/g. Polyol X isall PO tipped.

[0058] 42. Polyol Y is a polyether polyol made by propoxylated glyceroland typically with 7% ethylene oxide. It has a hydroxyl value of 55 mgKOH/gm and is ethylene oxide tipped triol;

[0059] 43. Polycat 46 is 38% potassium acetate in ethyleneglycol(hydroxyl values 68.7), a strong trimer catalyst from Air Productsand Chemicals, Allentown, Pa.;

[0060] 44. PPG is polypropylene glycol;

[0061] 45. PPG 200 is propylene glycol having a molecular weight of 200from ARCO Chemical;

[0062] 46. PPG 425 is propylene glycol having a molecular weight of 425from ARCO Chemical;

[0063] 47. PPG 1000 is propylene glycol having a molecular weight of1000 from ARCO Chemical;

[0064] 48. PPG 2000 is propylene glycol having a molecular weight of2000 from ARCO Chemical;

[0065] 49. Rucoflex S-2011-35 is a polyester polyol from RucoCorporation, Hicksville, N.Y. having a molecular weight of 3000, a OHvalue of 35 and a functionality of 2.0

[0066] 50. Rucoflex S-2011-35 is a polyester polyol from RucoCorporation, Hicksville, N.Y. having a molecular weight of 2000, a OHvalue of 55 and a functionality of 2.0

[0067] 51. Rucoflex S-2011-35 is a polyester polyol from RucoCorporation, Hicksville, N.Y. having a molecular weight of 1000, a OHvalue of 110 and a functionality of 2.0

[0068] 52. Stepanpol SP-1752 from Stepan Corporation, Northfield, Ill.60093, is a diethylene glycol/orthophthalate polyester polyol having anaverage molecular weight (g/mol) of 640, a functionality of 2.0, and ahydroxyl value of 640 mg KOH/gm

[0069] 53. TEG is triethylene glycol;

[0070] 54. UAX 1075 is a blocked amine catalyst from OSI Specialties;

[0071] 55. Unitol DSR from Unichem, Chicago, Ill. is a fatty acidderivative of oleic acid and linoleic acid.

[0072] 56. Wurtz INT 6871 is an internal mold release agent forpolyurethane foams from Wurtz, Bingen-Sponsheim, Germany;

[0073] 57. Wurtz PAT 672 is an internal mold release agent forpolyurethane rigid foams from Wurtz, Bingen-Sponsheim, Germany;

[0074] 58. Molecular weight is number average.

POLYISOCYANURATE SYSTEMS

[0075] The isocyanates employed in the polyisocyanurate systems of theinvention typically have viscosities of from about 50 to about 1500centipoise(“cps”), preferably about 50 to about 400 cps.

[0076] Isocyanate prepolymers may also be employed in thepolyisocyanurate systems of the invention. Useful prepolymers which maybe employed have a NCO value of from about 9 to about 26, preferablyabout 10 to about 26. Useful isocyanate prepolymers may be based on anyof toluene diisocyanate, naphthalene diisocyante, hexamethylenediisocyante, MDI, hydrogenated MDI, and tetramethylxylene diisocyante.

[0077] The polyols employed in the polyisocyanurate systems of theinvention typically have a viscosity of about 200 to about 8500 cps,preferably about 400 cps to about 1000 cps.

[0078] Useful polyols include polyether polyols and polyester polyols.Polyether polyols include those prepared by reacting alkylene oxides,aromatic-substituted alkylene oxides or mixtures thereof with an activehydrogen-containing initiator compound. Suitable oxides include ethyleneoxide, propylene oxide, 1,2-butylene oxide, styrene oxide,epichlorohydrin, epibromohydrin, and mixtures thereof. Suitableinitiator compounds include water, ethylene glycol, propylene glycol,butanediol, hexanediol, glycerine, trimethylol propane, pentaerythritol,hexanetriol, sorbitol, sucrose, hydroquinone, resorcinol, catechol,bisphenols, novolac resins, phosphoric acid and mixtures thereof. Othersuitable initiators further include, for example, ammonia,ethylenediamine, diaminopropanes, diaminobutanes, diaminopentanes,diaminohexanes, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentamethylenehexamine, ethanolamine,aminoethylethanolamine, aniline, 2,4-toluenediamine, 2,6-toluenediamine,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,1,3-phenylenediamine, 1,4-phenylenediamine, naphthylene-1,5-diamine,triphenylmethane 4,4′,4″-triamine, 4,4′-di(methylamino)diphenylmethane,1,3-diethyl-2,4-diaminobenzene, 2,4-diaminomesitylene,1-methyl-3,5-diethyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,6-diaminobenzene,1,3,5-triethyl-2,6-diaminobenzene,3,5,3′,5′-tetra-ethyl-4,4′-diamino-diphenylmethane, and amine aldehydecondensation products such as the polyphenylpolymethylene polyaminesproduced from aniline and formaldehyde and mixtures thereof.

[0079] Useful polyester polyols which may be employed include thoseprepared by reacting a polycarboxylic acid or anhydride with apolyhydric alcohol. The polycarboxylic acids may be aliphatic,cycloaliphatic, aromatic and/or heterocyclic and may be substituted(e.g., with halogen atoms) and/or unsaturated. Examples of suitablecarboxylic acids and anhydrides include succinic acid; adipic acid;suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalicacid; terephthalic acid; trimellitic acid; phthalic acid anhydride;tetrahydrophthalic acid anhydride; hexahydrophthalic acid anhydride;tetrachlorophthalic acid anhydride; endomethylene tetrahydrophtalic acidanhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride;fumaric acid; dimeric and trimeric fatty acids, such as those of oleicacid, which may be in admixture with monomeric fatty acids. Simpleesters of polycarboxylic acids may also be used as starting materialsfor polyester polyols, such as terephthalic acid dimethyl ester,terephthalic acid bisglycol ester and mixtures thereof.

[0080] Useful weight ratios of isocyanate to polyol in thepolyisocyanurate systems of the invention vary from about 0.3 to about9.0, preferably about 0.6 to about 6.0, more preferably about 0.8 toabout 1.2.

[0081] In order to cure the polyisocyanurate systems during pultrusionand to obtain good conversion to polyisocyanurate, a catalyst capable ofinitiating both a urethane and an isocyanurate reaction is included inthe polyol component. Advantageously, catalysts in very small amounts ofless than about one percent by weight based on the total weight of thepolyol component may be used. Useful catalysts include tin salts such asstannous octoate and dibutyl tin dilaurate, tertiary amines such asdiaminobicyclooctane, N,N dimethylcyclohexyl amine, N-methylmorphine,and N-methylimidazole, alkali carboxylates such as potassium2-ethylhexanoate, potassium tetraalkylammonium carboxylates, sodium2-ethylhexanoate, and sodium tetraalkylammonium carboxylate, andalkaline earth carboxylates such as strontium 2-ethylhexanoate andstrontium tetraalkylammonium carboxylate. Alkali carboxylates arepreferred.

Type I Polyisocyanurate Systems

[0082] Type I polyisocyanurate systems which include a polyol componenthaving a chain extender and a catalyst, and an isocyanate component areformulated by blending. In Type I systems, the polyol may be present inan amount of up to about 1-99% and the chain extender may be present inan amount of up to about 1-99% based on total weight of the polyolcomponent.

[0083] The polyols used in Type I polyisocyanurate systems typicallyhave a molecular weight of about 300-6000, preferably about 1000 toabout 6000 and a functionality of about 2 to about 4. More preferably,the polyols have a functionality of about 2 to about 3 and a molecularweight of about 2000 to 6000.

[0084] Polyols employed in Type I polyisocyanurate systems typically arepolyethylene oxide capped polypropylene oxide polyether polyols havingabout 10 wt. % to about 50 wt. % ethylene oxide, a functionality ofabout 2, and a hydroxyl value of about 30 mg KOH/gm. These polyols arewell known in the art and are commercially available. Examples of thesepolyols include Polyol A, Polyol B, Polyol C, Polyol D, Polyol E andPolyol F as defined above. Polyols such as Polyols A-F can be made bythe addition of alkylene oxides such as ethylene and propylene oxideonto alcohols and amines which serve as initiators. Examples of theseinitiators include glycerol, DPG, and MEG.

[0085] Chain extenders which can be used in Type I polyisocyanuratesystems include glycerols and diols which have at least 2 hydroxylgroups and a MW less than about 300. Useful chain extenders includeglycerols and diols which have primary hydroxyl groups, glycerols anddiols which have secondary hydroxyl groups and glycerols and diols whichhave both primary and secondary hydroxyl groups. Preferably, the chainextenders are glycerols and diols which have secondary hydroxyl groupsand a molecular weight of more than about 62. Examples of these chainextenders include but are not limited to DEG, TEG, 2,3 BD, 1,2 PD, andDPG, preferably 1,2 PD and DPG.

[0086] Various additives may be included in the polyol componentemployed in Type I and Type II polyisocyanurate systems to controlshrinking, color, mechanical properties, and fire retardance and releaseproperties. Useful release agents include but are not limited to fattyamides such as erucamide or stearamide, fatty acids such as oleic acid,-amino oleic acid, fatty esters such as Loxiol G71S, carnuba wax,beeswax (natural esters), butyl stearate, octyl stearate, ethyleneglycol monostearate, ethylene glycol distearate and glycerinemonooleate, and esters of polycarboxylic acids with long chain aliphaticmonovalent alcohols such as dioctal sebacate, mixtures of (a) mixedesters of aliphatic polyols, dicarboxylic acids and long-chainedaliphatic monocarboxylic acids, and (b) esters of the groups: (1) estersof dicarboxylic acids and long-chained aliphatic monofunctionalalcohols, (2) esters of long-chained aliphatic monofunctional alcoholsand long-chained aliphatic monofunctional carboxylic acids, (3) completeor partial esters of aliphatic polyols and long-chained aliphaticmonocarboxylic acids, in a tratio of (a) to (b) of from 1:3 to 9:1;silicones such as Tegostab L1-421T, Kemester 5721, metal carboxylatessuch as zinc stearate and calcium stearate, waxes such as montan wax andchlorinated waxes, fluorine containing compounds such aspolytetrafluoroethylene, phosphates and chlorinated phosphates.

[0087] Useful additives for control of mechanical properties includecalcium carbonate, barium sulfate, clay, aluminum trihydrate, antimonyoxide, milled glass fibers, wollastonite, talc, mica, etc. Theseadditives can be included in and added to the polyol component inamounts of up to about 65% based on the total weight of the polyolcomponent.

[0088] In Type I polyisocyanurate systems, the isocyanate component maybe any of 2,4′MDI, 4,4′MDI, polymeric MDI, blocked isocyanate, andternary blends thereof. Examples of useful isocyanates includeisocyanates A-D as defined above. Typically, ternary isocyanate blendssuch as isocyanate C and isocyanate D are prepared by mixing a standardpolymeric MDI with a blend of 2,4′ MDI and 4,4′ MDI. Standard polymericMDI is a mixture of functionality 2 and higher species such that theaverage functionality is about 2.5 to 2.8. See (G. Woods., The ICIPolyurethanes Book, sec. ed. John Wiley, N.Y. 1990, page 34-35).

[0089] In Type I polyisocyanurate systems, the polyol, chain extenderand isocyanate may be varied to control the miscibility of the reactionmixture formed. Generally, for an isocyanate having a given 2,4′-MDIcontent, the miscibility of the polyol component-isocyanate reactionmixture may be increased by using polyols which have higher amounts ofethylene oxide (“EO”)content. Polyols with higher ethylene oxidecontents up to about 50% ethylene oxide content are preferred. Chainextenders which have higher levels of secondary hydroxyls also may beused to increase the miscibility of the reaction mixture. Chainextenders which have secondary hydroxyls and a molecular weight greaterthan 62 are preferred. Isocyanates with higher amounts of 2,4′-MDI arepreferred to achieve increased miscibility.

Type II Polyisocyanurate Systems

[0090] In Type II polyisocyanurate systems, the isocyanate component maybe any of 2,4′MDI, 4,4′MDI, polymeric MDI, and blends thereof. Examplesof useful isocyanates include isocyanates A-D as defined above.Typically, ternary isocyanate blends such as isocyanate C and isocyanateD are prepared by mixing a standard polymeric MDI with a blend of 2,4′MDI and 4,4′ MDI.

[0091] Type II polyisocyanurate systems employ polyether polyols whichhave an EO content less than about 15 wt. % and a molecular weight ofabout 300-2000, preferably about 300-1000. The functionality of the lowEO polyether polyols employed is about 2 to about 6, preferably about 2to about 3, most preferably about 2. Examples of useful low EO polyetherpolyols include PPG 425, Polyol F, PPG 1000, PPG 2000 and Polyol D.Blends of low EO polyether polyols also can be used as the polyolcomponent. In this aspect, the MW of the individual polyether polyols isabout 175 to about 1000.

Pultrusion of Type I and Type II Polyisocyanurate Systems

[0092] Type I and Type II polyisocyanurate systems, preferably Type Isystems, may be used to produce pultruded neat polyisocyanurates as wellas pultruded polyisocyanurate composites.

[0093] Polyisocyanurate systems of the invention having indices of fromabout 200 to about 1000, preferably about 300 to about 600 may bepultruded. Polyisocyanurate systems which include fire retardantadditives may be pultruded at indices of about 300 to about 900.

[0094] The reaction mixtures formed from the polyisocyanurate systemsemployed in the invention have numerous advantages for use inpultrusion. These advantages include long pot life at ambienttemperatures, ability to be easily mixed, viscosities suitable for goodwet-out of the reinforcement material under resin injection conditions,good bonding with the reinforcement material even when unsized, andsnap-cure characteristics when heated to a specific temperature. Forexample, Type I and Type II polyisocyanurate systems at an index of fromabout 300 to about 900 are fully cured at about 120-140° C. in about 1minute with an isocyanate conversion of about 95%. The polyisocyanuratesystems employed in the invention can be pultruded in the presence ofglass fiber reinforcement to produce glass fiber reinforced,polyisocyanurate composites and cured in-situ at elevated temperatures.

Miscibility Evaluation

[0095] In order to evaluate the miscibility of the polyisocyanuratesystems employed in the invention, one gram of isocyanate is placed on awatch glass. Then, the polyol component is added to achieve an index of650. The polyol component and the isocyanate are mixed by hand with aspatula for 30 seconds. The resulting reaction mixture is evaluated forclarity. If the reaction mixture is clear within 30 seconds after mixingis stopped, then the polyisocyanurate system is considered miscible.

[0096] The invention will now be further illustrated by reference to thefollowing non-limiting examples.

Type I Immiscible Polyisocyanurate Systems EXAMPLE 1

[0097] The following components are blended where all amounts are inparts by weight. Polyol Component Amount Polyol A 100 MEG 6.76

[0098] After mixing is finished, it took 500 seconds before the mixturebecame transparent. The system is therefore immiscible.

Type I Miscible Polyisocyanurate Systems EXAMPLE 2

[0099] The procedure of example 1 is repeated except that DPG issubstituted for MEG as a chain extender. The amount of DPG is such thatthe molar amount of chain extender is equal to that used in example 1.Also, Isocyanate D is substituted for isocyanate B. All amounts ofmaterials in the polyol component are parts by weight. Polyol ComponentAmount Polyol A 100 DPG 16.3

[0100] The mixture is optically transparent within thirty seconds aftermixing is stopped, indicating good system miscibility.

EXAMPLE 2A

[0101] The procedure of example 2 is repeated except with the followingamounts of the components, where all amounts of the materials in thepolyol component are expressed in wt % based on total weight of thepolyol component. The amount of the Dabco T45 catalyst is based on thetotal weight of the polyol component. Polyol Component Amount Polyol A86.40 TEG 13.60 Total 100.00

EXAMPLE 2B

[0102] The following components are blended where all amounts are inweight % based on the total weight of the polyol component. Theisocyanate and polyol component components are uniformly mixed at roomtemperature in a static mixer. Polyol Component Amount Polyol A 87.5 DPG12.5 Total 100.00

EXAMPLE 2C

[0103] The procedure of example 2B is repeated except with the followingamounts of the components, where all amounts of materials in the polyolcomponent are expressed in wt. % based on total weight of the polyolcomponent. The amount of the catalyst is based on the total weight ofthe polyol component. Polyol Component Amount Polyol A 90.30 2,3 BD 9.70Total 100.00

EXAMPLE 2D

[0104] The procedure of example 2B is repeated except with the followingamounts of the components, where all amounts of materials in the polyolcomponent are expressed in wt. % based on total weight of the polyolcomponent. The amount of the catalyst is based on the total weight ofthe polyol component. Polyol Component Amount Polyol A 92.50 1,2 PD 7.50Total 100.00

EXAMPLE 2E

[0105] The procedure of example 2B is repeated except with the followingamounts of the components, where all amounts of the materials in thepolyol component are expressed in wt. % based on total weight of thepolyol component. The amount of the catalyst is based on the totalweight of the polyol component. Polyol Component Amount Polyol A 91.20 2m 1,3 PD 8.80 Total 100.00

Type II Miscible Polyisocyanurate Systems EXAMPLE 2F

[0106] The following components are blended to provide a reactionmixture.

[0107] Polyol: PPG425

[0108] Isocyanate D

[0109] Isocyanate index=450

[0110] The mixture is optically transparent within 30 seconds aftermixing is stopped indicating good system miscibility.

Evaluation of Cure Characteristics

[0111] To evaluate cure characteristics of the polyisocyanurate systems,the polyol component and isocyanate components of the polyisocyanuratesystems are mixed manually in a paper cup for about 20 seconds and thenpoured into a glass vial. The glass vial accommodates approximately 5 gof the sample. A mark is placed on the vial so as to repeat the amountof polyisocyanurate system added to the vial to an accurate extent.

[0112] The glass vial is placed in a heated oil bath to ensureconsistent temperature. The components themselves are not heated and areat room temperature when placed into the glass vial. A vibrating needle(Polymer labs UK) is placed into the glass vial to estimate theviscosity of the mixture. As the reaction proceeds, the viscosity of themixture increases and is recorded by the vibrating needle connected to apen recorder. The time when the viscosity increases steeply is taken asthe gel time. The gel time is given in seconds.

[0113] This test procedure is repeated for different polyisocyanuratesystems having differing catalyst levels, different oil bathtemperatures, and different isocyanate indices.

Gel Times of Type I Immiscible Polyisocyanurate Systems EXAMPLES3A-3L

[0114] In each of Examples 3A-3L, the gel time of the immiscible systemof Example 1 is measured as a function of catalyst concentration and oilbath temperature. As a catalyst, a mixture of Dabco T45, Dabco T12 andDabco TMR at a weight ratio of 35.0 to 3.5 to 61.5 is used. As inexample 1, the isocyanate index is 650. The results are shown below inTable 1. TABLE 1 Catalyst amount Example Bath Temp° C. Wt % Gel Time(sec) 3A 23 0.125 approx. 600 3B 55 0.125 90 3C 85 0.125 60 3D 124 0.12530 3E 23 0.25 84 3F 55 0.25 55 3G 85 0.25 50 3H 124 0.25 24 3I 23 0.5036 3J 55 0.50 28 3K 85 0.50 24 3L 124 0.50 20

Gel Times of Type I Miscible Polyisocyanurate Systems EXAMPLES 4A-4P AND4AA-4LL

[0115] The miscible system of Example 2 is modified to include Dabco T45catalyst. In each of these examples, the gel time of is measured as afunction of the catalyst concentration and oil bath temperature. This isdone at isocyanate indices 650 and 450. The gel times are shown inTables 2 and 2A. TABLE 2 Gel times at Isocyanate index 650 Example OilBath Temp° C. Dabco T45 Wt % Gel Time (sec) 4A 23 0.1 approx. 600 4B 500.1 145 4C 80 0.1 58 4D 120 0.1 35 4E 150 0.1 20 4F 23 0.125 145 4G 500.125 50 4H 80 0.125 45 4I 120 0.125 30 4J 150 0.125 <15 4K 23 0.25 304L 50 0.25 25 4M 80 0.25 25 4N 120 0.25 20 4P 150 0.25 <15

[0116] TABLE 2A Gel times at Isocyanate Index 450 Example Oil Bath Temp°C. Catalyst amount Wt % Gel Time (sec) 4AA 23 0.15 approx. 600 4BB 550.15 180 4CC 80 0.15 80 4DD 120 0.15 40 4EE 23 0.2 420 4FF 55 0.2 1104GG 80 0.2 60 4HH 120 0.2 40 4II 23 0.25 200 4JJ 55 0.25 80 4KK 80 0.2545 4LL 120 0.25 30

Gel Times of Type II Miscible Polyisocyanurate Systems EXAMPLES 5A-5E

[0117] In each of examples 5A-5E, the gel time of the system describedin Example 2F is measured a function of oil bath temperature. Theisocyanate index is 450. Dabco T45 catalyst in an amount of of 0.1weight % based on the total weight of the polyol component as added tothe polyol component. The results are shown in Table 3. TABLE 3 ExampleBath Temp° C. Gel Time (sec) 5A 25 >500 5B 50 130 5C 80 50 5D 120 40 5E150 20

Effect of EO content of Polyol on Miscibility of Type I PolyisocyanurateSystems EXAMPLES 6A-6AA

[0118] In each of examples 6A-6AA, the effect of EO content of thepolyol on the miscibility of Example 2 is illustrated in Table 4. TABLE4 Effect of EO Content of Polyol Amount % EO in Chain of Chain EX PolyolPolyol Extender Extender¹ Isocyanate Index Result² 6A Polyol C 50.0 MEG5.63 Isocyanate B 650 I 6B Polyol C 50.0 DEG 9.62 Isocyanate B 650 M 6CPolyol C 50.0 TEG 13.6 Isocyanate B 650 M 6D Polyol C 50.0 1,4BD 8.16Isocyanate B 650 I 6E Polyol C 50.0 1,3BD 8.16 Isocyanate B 650 I 6FPolyol C 50.0 2,3BD 8.16 Isocyanate B 650 M 6G Polyol C 50.0 1,2PD 8.16Isocyanate B 650 M 6H Polyol C 50.0 DPG 12.23 Isocyanate B 650 M 6IPolyol C 50.0 2 ml, 3PD 8.16 Isocyanate B 650 I 6J Polyol B 27.0 MEG5.63 Isocyanate B 650 I 6K Polyol B 27.0 DEG 9.62 Isocyanate B 650 I 6LPolyol B 27.0 TEG 13.6 Isocyanate B 650 I 6M Polyol B 27.0 1,4BD 8.16Isocyanate B 650 I 6N Polyol B 27.0 1,3BD 8.16 Isocyanate B 650 I 6OPolyol B 27.0 2,3BD 8.16 Isocyanate B 650 I 6P Polyol B 27.0 1,2PD 8.16Isocyanate B 650 I 6Q Polyol B 27.0 DPG 12.23 Isocyanate B 650 I 6RPolyol B 27.0 2 ml, 3PD 8.16 Isocyanate B 650 I 6S Polyol A 21.0 MEG5.63 Isocyanate B 650 I 6T Polyol A 21.0 DEG 9.62 Isocyanate B 650 I 6UPolyol A 21.0 TEG 13.60 Isocyanate B 650 I 6V Polyol A 21.0 1,4BD 8.16Isocyanate B 650 I 6W Polyol A 21.0 1,3BD 8.16 Isocyanate B 650 I 6XPolyol A 21.0 2,3BD 8.16 Isocyanate B 650 I 6Y Polyol A 21.0 1,2PD 8.16Isocyanate B 650 I 6Z Polyol A 21.0 DPG 12.23 Isocyanate B 650 I 6AAPolyol A 21.0 2 ml, 3PD 8.16 Isocyanate B 650 I

Effect of 2,4 MDI Content of Isocyanate on Miscibility of Type IPolyisocyanurate Systems EXAMPLES 7A-7AG

[0119] Examples 7A-7AG in Table 5 show the effect of 2,4′ MDI content onmiscibility of Type I polyisocyanurate systems. In each of theformulations shown in Table 5, the Index is 650. TABLE 5 Effect ofIsocyanate Composition on Miscibility of Type I Polyisocyanurate Systems%2,4′ MDI Chain Amount of in Ex- Chain EX Isocyanate Isocyanate tenderExtender¹ Polyol Result² 7A Isocyanate B 0 MEG 6.76 Polyol A I 7BIsocyanate B 0 DEG 11.32 Polyol A I 7C Isocyanate B 0 TEG 16.01 Polyol AI 7D Isocyanate B 0 1,4BD 9.61 Polyol A I 7E Isocyanate B 0 1,3BD 9.61Polyol A I 7F Isocyanate B 0 2,3BD 9.61 Polyol A I 7G Isocyanate B 01,2PD 8.11 Polyol A I 7H Isocyanate B 0 DPG 14.39 Polyol A I

[0120] TABLE 5 Effect of Isocyanate Composition on Miscibility of Type IPolyisocyanurate Systems %2,4′ MDI Amount of in Chain Chain EXIsocyanate Isocyanate Extender Extender¹ Polyol Result² 7I Isocyanate C9.4 2 ml, 3PD 9.61 Polyol A I 7J Isocyanate C 9.4 MEG 6.76 Polyol A I 7KIsocyanate C 9.4 DEG 11.32 Polyol A M 7L Isocyanate C 9.4 TEG 16.01Polyol A M 7M Isocyanate C 9.4 1,4BD 9.61 Polyol A I 7N Isocyanate C 9.41,3BD 9.61 Polyol A M 7O Isocyanate C 9.4 2,3BD 9.61 Polyol A M 7PIsocyanate C 9.4 1,2PD 8.11 Polyol A I 7Q Isocyanate C 9.4 DPG 14.39Polyol A M 7R Isocyanate C 9.4 2 ml, 3PD 9.61 Polyol A I 7S Isocyanate D19.5 MEG 5.63 Polyol A I 7T Isocyanate D 19.5 DEG 9.62 Polyol A M 7UIsocyanate D 19.5 TEG 13.60 Polyol A M 7V Isocyanate D 19.5 1,4BD 8.16Polyol A I 7AA Isocyanate D 19.5 1,3BD 8.16 Polyol A M 7BB Isocyanate D19.5 2,3BD 8.16 Polyol A M 7CC Isocyanate D 19.5 1,2PD 8.16 Polyol A M7DD Isocyanate D 19.5 DPG 12.23 Polyol A M 7EE Isocyanate D 19.5 2 ml,3PD 8.16 Polyol A M 7FF Isocyanate B 0 MEG 6.76 Polyol B I 7GGIsocyanate B 0 DEG 11.32 Polyol B I 7HH Isocyanate B 0 TEG 16.01 PolyolB I 7II Isocyanate B 0 1,4BD 9.61 Polyol B I 7JJ Isocyanate B 0 1,3BD9.61 Polyol B I 7KK Isocyanate B 0 2,3BD 9.61 Polyol B I 7LL IsocyanateB 0 1,2PD 8.11 Polyol B I 7MM Isocyanate B 0 DPG 14.39 Polyol B I 7NNIsocyanate C 9.4 2 ml, 3PD 9.61 Polyol B I 7OO Isocyanate C 9.4 MEG 6.76Polyol B I 7PP Isocyanate C 9.4 DEG 11.32 Polyol B M 7QQ Isocyanate C9.4 TEG 16.01 Polyol B M 7RR Isocyanate C 9.4 1,4BD 9.61 Polyol B I 7SSIsocyanate C 9.4 1,3BD 9.61 Polyol B I 7TT Isocyanate C 9.4 2,3BD 9.61Polyol B I 7UU Isocyanate C 9.4 1,2PD 8.11 Polyol B I 7VV Isocyanate C9.4 DPG 14.39 Polyol B M 7WW Isocyanate C 9.4 2 ml, 3PD 9.61 Polyol B I7XX Isocyanate D 19.5 MEG 5.63 Polyol B I 7YY Isocyanate D 19.5 DEG 9.62Polyol B M 7ZZ Isocyanate D 19.5 TEG 13.60 Polyol B M 7AB Isocyanate D19.5 1,4BD 8.16 Polyol B M 7AC Isocyanate D 19.5 1,3BD 8.16 Polyol B M7AD Isocyanate D 19.5 2,3BD 8.16 Polyol B M 7AE Isocyanate D 19.5 1,2PD8.16 Polyol B M 7AF Isocyanate D 19.5 DPG 12.23 Polyol B M 7AGIsocyanate D 19.5 2 ml, 3PD 8.16 Polyol B M

Effect of PO Content of Polyol on Miscible of Type II PolyisocyanurateSystems EXAMPLES 8A-8A41

[0121] Examples 8A-8A41 show the effect of polyol on the miscibility ofType II polyisocyanurate systems. Miscibility is evaluated using themiscibility test disclosed above. The results are shown in Table 6.TABLE 6 Effect of Polyol on Miscibility of Type II PolyisocyanuratesSystems Wt. Of % PO Polyol/gm Example Polyol FN Content OHV Isocyanate DResult¹ 8T Polyol A 2 79 30 0.5 M 8U Polyol C 3 50 48 0.5 M 8V DPG 2 100830 0.7 I 8W PPG 200 2 100 561 0.7 I 8X PPG 425 2 100 250 0.7 M 8Y PPG1000 2 100 107 0.7 M 8Z PPG 2000 2 100 56.1 0.7 M 8A1 Polyol D 3 90 560.7 M 8A2 Polyol F 3 100 28 0.7 M 8A3 Polyol E 3 83 35 0.7 M 8A4 PolyolA 2 79 30 0.7 M 8A5 DPG 2 100 830 1 I 8A6 PPG 200 2 100 561 1 I 8A7 PPG425 2 100 250 1 M 8A8 PPG 1000 2 100 107 1 M 8A9 PPG 2000 2 100 56.1 1 I8A10 Polyol D 3 90 56 1 I 8A11 Polyol F 3 100 28 1 I 8A12 Polyol E 3 8335 1 I 8A13 Polyol A 2 79 30 1 M 8A14 Polyol C 3 50 48 1 M 8A15 DPG 2100 830 0.1 I 8A16 PPG 200 2 100 561 0.1 I 8A17 PPG 425 2 100 250 0.1 M8A18 PPG 1000 2 100 107 0.1 M 8A19 PPG 2000 2 100 56.1 0.1 M 8A20 PolyolD 3 90 56 0.1 M 8A21 Polyol F 3 100 28 0.1 M 8A22 Polyol E 3 83 35 0.1 M8A23 Polyol A 2 79 30 0.1 M 8A24 DPG 2 100 830 0.5 I 8A25 PPG 200 2 100561 0.5 I 8A26 PPG 425 2 100 250 0.5 M 8A27 PPG 1000 2 100 107 0.5 M8A28 PPG 2000 2 100 56.1 0.5 M 8A29 Polyol D 3 90 56 0.5 I 8A30 Polyol F3 100 28 0.5 I 8A31 Polyol E 3 83 35 0.5 I 8A32 Polyol A 2 79 30 0.5 I8A33 Polyol C 3 50 48 0.5 M 8A34 DPG 2 100 830 1 I 8A35 PPG 200 2 100561 1 I 8A36 PPG 425 2 100 250 1 M 8A37 PPG 1000 2 100 107 1 I 8A38 PPG2000 2 100 56.1 1 I 8A39 Polyol D 3 90 56 1 I 8A40 Polyol F 3 100 28 1 I8A41 Polyol E 3 83 35 1 I

EXAMPLES A-D

[0122] Examples A-D illustrate the use of polyester polyols inpolyisocyanurate systems that may be used in manufacture of pultrudedpolyisocyanurates and reinforced pultruded polyisocyanurate matrixcomposites.

EXAMPLE A

[0123] The following components are blended where all amounts are inparts by weight. Polyol Component Parts by weight Polyol G 100.0 DabcoT-45 0.4 DEG 12.0 Total 112.4

EXAMPLE B

[0124] The following components are blended where all amounts are inparts by weight. Polyol Component Parts by weight Rucoflex S-2011-35100.0 Dabco T-45 0.4 MEG 12.0 112.4

EXAMPLE C

[0125] The following components are blended where all amounts are inparts by weight. Polyol Component Parts by weight Rucoflex S-2011-55100.0 Dabco T-45 0.4 DPG 6.0 106.4

EXAMPLE D

[0126] The following components are blended where all amounts are inparts by weight. Polyol Component Parts by weight Stepanpol SP-1752100.0 Dabco T-45 0.4 DPG 4.0 104.4

Mechanical Properties of Neat Polyisocyanurates

[0127] Dried and degassed isocyanates and polyol components are employedto produce neat polyisocyanurate castings. The polyol component isrotovaped at 16 mbar and 80° C. for 2 hours. The isocyanate is placedunder full vacuum for 1 hour while stirring. Neat polyisocyanuratecastings are produced by mixing the dried and degassed isocyanate andpolyol components in a paper cup with a spatula. A thin layer of theresulting reaction mixture is poured into a Teflon based mold. Thislayer is placed under vacuum in a desiccator for 3 minutes and thencured in a preheated oven at 150° C. to yield a casting. Samples are cutfrom the casting to determine the flexural modulus (ASTM 790) and impactstrength (unnotched charpy). The neat polyisocyanurate castings haveflexural strengths comparable to polyester, and have much greaterflexibility than polyester.

Type I Polyisocyanurates EXAMPLE 9

[0128] The composition of example 2 is modified to include 0.3 weight %Dabco T-45 catalyst based on total weight of the polyol component.Castings from the formulation are produced as above at an isocyanateindices of 300 and 500. The results are: Index 300 Index 500 FlexuralModulus (MPa) 690 1100 Impact Strength (kJ/m²) 54 24

Type II Polyisocyanurates EXAMPLE 10

[0129] The composition of example 2F is modified to include 0.3 weight %Dabco T-45 catalyst based on total weight of the polyol component. Acasting is produced at an isocyanate index of 500. The flexural modulusis 2700 MPa and the impact strength is 28 kJ/m².

PULTRUSION OF POLYISOCYANURATE SYSTEMS

[0130] Generally, pultrusion of neat polyisocyanurates and glass fiberreinforced polyisocyanurate composites, as well as neat polyurethanesand glass fiber reinforced polyurethane composites is performed bysupplying the isocyanate and polyol components to a mix metering machinefor delivery in a desired ratio to a static mixer to produce a reactionmixture. Fibers useful as reinforcements include glass fibers, aramidfibers such as nylon, Kevlar, carbonaceous fibers such as graphitefibers, metal fibers such as steel fibers, and natural fibers such aslignocellulosic fibers, hemp, and jute, preferably glass fibers.

[0131] During pultrusion, the polyol component and isocyanate used inthe polyisocyanurate systems of the invention are statically mixed toyield a reaction mixture suitable for use in pultrusion. Dynamic mixingmay be used provided that it does not generate heat in the resultingreaction mixture or entrain gas in the reaction mixture. Preferably,static mixing is used. When static mixing is employed, the static mixeris cooled, preferably to about 10° C. to 30° C., more preferably about15° C. At about 10-30° C., the polyisocyanurate system reaction mixturethoroughly wets the glass fiber reinforcement but does not convert topolyisocyanurate. At temperatures of about 10-30° C., the initiationtime of polyisocyanurate reaction of the polyisocyanurate reactionmixture is extended to at least 15 minutes.

[0132] The reaction mixture is supplied to an injection die where it canbe used to impregnate glass fibers being fed concurrently into theinjection die to produce a composite of fibers coated with thepolyisocyanurate reaction mixture. The reaction mixture and fibers arepresent in the injection die for very short time periods, typically lessthan about 50 seconds. The resulting composite is sent to a zoned curingdie having a desired cross-section of a pultrusion machine where it isat least partially cured and shaped. The gel time of thepolyisocyanurate reaction mixture that optionally includes catalysts andinternal mold release agents is sufficient to insure that the reactionmixture at least partially cures in the curing die.

[0133] Curing of the polyisocyanurate systems employed in the inventionentails a two step procedure wherein the polyisocyanurate systemreaction mixture is maintained at about 10° C. to about 30° C. toproduce polyurethanes and then heated to about 150° C. to producesnap-cured polyisocyanurates. During pultrusion, the fibers are pulledat a speed sufficient to ensure that the fibers are wetted by thereaction mixture supplied to the injection die. Similarly, the viscosityof the reaction mixture and the pressure at which the reaction mixtureis supplied to the injection die are sufficient to ensure that thefibers are wetted. Typically, the reaction mixture is supplied at apressure of about one to ten atmospheres. During pultrusion, thetemperature of the injection die temperature is sufficiently cool tomaintain the polyisocyanurate reaction mixture in a liquid state andbelow the isocyanurate reaction temperature.

[0134] During pultrusion, the systems employed in the invention canundergo substantial polymerization while in the injection die. In thiscontext, substantial polymerization is understood to mean that at least50% of the OH groups of the polyol component of the reaction mixture areutilized while the reaction mixture is in the injection die.

[0135] The pultruded composites produced by the invention have about10-90%, preferably about 20-80%, more preferably about 30-75% of fibersbased on the total weight of the composite.

[0136] In pultrusion of the polyisocyanurate systems employed in theinvention, the isocyanate and polyol components are supplied to a Cannon2-component RIM machine or a Liquid Control machine for metering ofthese components to a static mixer. The throughput of these machines isabout 4.5 gm/sec to about 40 gm/sec. The static mixers employed areequipped with 22 polypropylene elements or 24 nylon elements. The mixerscombine the isocyanate and polyol components to provide a reactionmixture for supply to the injection die of a pultrusion machine. Thestatic mixers vary from 9.0-9.4 mm diameter and from 185-190 mm long.

[0137] The pultrusion machines employed are either a Pulstar 2408machine from Owens-Corning Fiberglass Co., Grainville, Ohio or a PultrexP8000 machine from Pultrex, Ltd., England. These machines employ areciprocating type puller. These machines are also equipped with aclosed injection die and a zoned curing die that is in direct contactwith the injection die. The injection die is 220 mm long. The closedinjection die preferably is that shown in U.S. Pat. No. 5783013, theteachings of which are incorporated by reference herein in theirentirety. The closed injection die is capable of concurrent receipt offiber reinforcement and the polyol-isocyanate reaction mixture. Thecuring die measures 1050 mm×180 mm×80 mm whereas the cavity formed bythe curing die measures 1050 mm×100 mm×3 mm. That portion of the curingdie that contacts the injection die is equipped with cooling coils tomaintain the polyisocyanurate system reaction mixture at about 4-10° C.

[0138] The zoned curing die is equipped with electrical heating coils.Each of the coils is attached to a separate controller so that thefront, middle and end portions of the curing die are maintained atdesired temperatures.

[0139] During pultrusion of the polyisocyanurate systems employed in theinvention, the reaction mixture is supplied from the static mixer atabout 1-10 atm. to the injection die while glass fiber reinforcement issupplied to the die at a rate of about 0.3-1.6 m/min. The glass fiberreinforcement is supplied to the injection die in the form of glassrovings and mats to achieve about a 50-55 weight % of glassreinforcement in the pultruded polyisocyanurate composite. Typically,the glass fiber reinforcement is supplied in the form of six rovings ontop, 48 rovings in the middle, and 6 rovings on the bottom. A glassfiber mat is present between the top roving and middle roving. A glassfiber mat also is present between the middle roving and the bottomroving. Typical pull speeds during pultrusion are about 0.3-1.6 meterper minute and typical pull forces are about 1-20 kilo newton.

[0140] The flexural strength of the pultruded glass fiber reinforcedpolyisocyanurate composite can be controlled by varying the weightpercent of isocyanate in the polyisocyanurate formulation. Generally,the flexural strength of the pultruded polyisocyanurate compositesproduced with TYPE I and TYPE II systems is increased by decreasing theamount of isocyanate in the formulation.

Pultrusion of TYPE I Polyisocyanurate Systems EXAMPLE 11

[0141] This example illustrates pultrusion of glass fiber reinforcedType I immiscible polyisocyanurate system. The isocyanate and polyolcomponents are given below. The polyol component is made by mixing theindicated ingredients in the amounts shown. The amounts of theingredients employed in the polyol component are expressed in wt.percent based on the total weight of the polyol component. PolyolComponent Amount (wt. %) Polyol A 87.994 MEG 5.923 Dabco T-12 0.010Dabco T-45 0.443 Loxiol G71S 5.130 Kemeister 5721 0.500 Total 100.000

[0142] The polyol component at a temperature of 20° C., and theisocyanate at a temperature of 20° C. are supplied to the static mixerto produce a uniform reaction mixture. The reaction mixture is suppliedunder a pressure of 3.06 atm. from the mixer to the closed injection diewhile glass fiber reinforcement is supplied to the die at 350 mm/min.The temperature of the injection die is 15 C. The glass fiberreinforcement is supplied to the die in the form of glass rovings andmats to achieve 50% by weight of glass reinforcement in the pultrudedpolyisocyanurate composite. The glass fiber reinforcement is supplied inthe form of six rovings on top, 48 rovings in the middle, and 6 rovingson the bottom. A glass fiber mat is present between the top roving andmiddle roving. The composite is sent to the curing die for curing. Thecuring die has a temperature profile of 260 C front section, 260 Cmiddle section, and 260 C end section. Using a pull speed of 350 mm perminute and a pull force of 1 kilo newton, one meter of glass fiberreinforced polyisocyanurate material is pultruded during a period of 120seconds.

EXAMPLE 12

[0143] This example illustrates pultrusion of a fiber reinforcedpultruded polyisocyanurate type I miscible system using the polyolcomponent given below, where all amounts are in parts by weight is made.Polyol Component Amount Polyol A 87.4 DPG 12.6 Dabco T-45 0.33 LUWAX OPpowder 4.7 Wurtz INT 6871 4.7 TOTAL: 109.73

[0144] The machine settings and glass loadings are similar to thosedescribed in pultrusion example 11 with the exception that the supplypressure from the static mixer to the injection die is 4.76 atm. and therate of glass fibre supply is 0.82 m/min. The temperature of theinjection die is 10° C. The composite is sent to the curing die forcuring. The curing die has a temperature profile of 140° C. frontsection, 140° C. middle section, and 140° C. end section. Using a pullspeed of 0.5 mm/min and a pull force of 10 kN, 30 meters of glass fibrereinforced polyisocyanurate is pultruded during a period of one hour.

[0145] On the pultruded polyisocyanurate parts the flexural modulus isdetermined to be 24 GPa as determined by test method BS2782, pt10: MTD1005 (1977. The inter laminar shear strength of the pultruded part is 33MPA as determined by test method BS2783, pt3: MTD 341A (1977). The voidcontent as determined by test method BS EN 2564 is 2.2%.

EXAMPLE 13

[0146] The isocyanate and polyol components below are supplied to thestatic mixer described above to produce a reaction mixture. All amountsin the polyol component are in parts by weight. Polyol Component Partsby Weight Polyol A 87.4 DPG 12.6 Dabco T-45 0.38 LuWax OP 4.7 Wurtz PAT672 4.7 109.78

[0147] The reaction mixture is supplied to the above-describedpultrusion machine equipped with the above-described injection die andcuring die. Reinforcement in the form of glass fibers is supplied to theinjection die to achieve a glass fiber loading of about 56% glass byvolume (68 tows, 1 continuous strand mat@450 g/m, and one continuousstrand mat at 300 g/m). The injection die is maintained at 10° C., andthe front, middle and end zones of the curing die each are at 140° C.The pull speed of the fibers is 0.1 m/min. Under these conditions, 762cm of pultruded composite are formed over a period of 720 seconds.

EXAMPLE 14

[0148] The method of example 13 is repeated except that Wurtz INT 6871is substituted for LuWax OP and Wurtz PAT 672. In addition, the amountof Dabco T-45 catalyst is reduced from 0.38 parts to 0.33 parts. PolyolComponent Parts by Weight Polyol A 87.4 DPG 12.6 Dabco T-45 0.33 WurtzINT 6871 9.4 109.73

[0149] The reaction mixture is supplied to the above-describedpultrusion machine equipped with the above-described injection die andcuring die. Reinforcement in the form of glass fibers is supplied to theinjection die to achieve a glass fiber loading of about 42% glass byvolume (48 tows, 2 continuous strand mats@450 g/m). The injection die ismaintained at 10° C., and the front, middle and end zones of the curingdie are at 140° C. The pull speed of the fibers is 0.5 m/min. Underthese conditions, 82.3 meters of pultruded composite are formed over aperiod of 3 hours.

EXAMPLE 15

[0150] The method of example 14 is repeated except that LuWax OP isincluded in the polyol component as shown below. Polyol Component Partsby Weight Polyol A 87.4 DPG 12.6 Dabco T 45 0.33 LuWax OP 4.7 Wurtz INT6871 4.7 109.73 Isocyanate:Isocyanate D 135 parts to 100 parts of thepolyol component (450 Index)

[0151] The reaction mixture is supplied to the above-describedpultrusion machine equipped with the above-described injection die andcuring die. Reinforcement in the form of glass fibers is supplied to theinjection die to achieve a glass fiber loading of about 42% glass byvolume (46 tows, 2 continuous strand mats@300 g/m, 8 textured tows). Theinjection die is maintained at 10° C., and the front, middle and endzones of the curing die are at 140° C. The pull speed of the fibers is0.2 m/min. Under these conditions, 177.8 cm of pultruded composite areformed over a period of 600 seconds.

EXAMPLE 16

[0152] The method of example 15 is repeated except that Wurtz INT 6871in the amount shown below is used in the POLYOL component. PolyolComponent Parts by Weight Polyol A 87.4 DPG 12.6 Dabco T-45 0.33 LuWaxOP 4.7 Wurtz INT 6871 9.4 114.43 Isocyanate:Isocyanate D 135 parts to100 parts of the polyol component (450 Index)

[0153] The reaction mixture is supplied to the above-describedpultrusion machine equipped with the above-described injection die andcuring die. Reinforcement in the form of glass fibers is supplied to theinjection die to achieve a glass fiber loading of about 42% glass byvolume (62 tows, 2 continuous strand mats@300 g/m, 8 textured tows). Theinjection die is maintained at 10° C., and the front, middle and endzones of the curing die are at 160° C., 140° C. and 140° C.respectively. The pull speed of the fibers is 1.4 m/min. Under theseconditions, 153.62 meters of pultruded composite are formed over aperiod of two hours.

EXAMPLE 17

[0154] In this example, the polyol component includes motor oil andLoxiol G71 S as internal mold release agents. Polyol Component Parts byWeight Polyol A 87.4 DPG 12.6 Dabco T-45 0.38 Loxiol G71S 8.0 Motor Oil8.0 116.38 Isocyanate:Isocyanate D Index: 450.

[0155] The reaction mixture is supplied to the above-describedpultrusion machine equipped with the above-described injection die andcuring die. Reinforcement in the form of glass fibers is supplied to theinjection die to achieve a glass fiber loading of about 42% glass byvolume (60 tows, 2 continuous strand mats@300 g/m, 8 textured tows). Theinjection die is maintained at 10° C., and the front, middle and endzones of the curing die are at 140° C., 140° C. and 140° C respectively.The pull speed of the fibers is 0.1 m/min. Under these conditions,330.98 meters of pultruded composite are formed over a period of fourhours. The physical properties of the pultruded composite are shown inTable 7. TABLE 7 Physical Properties of PIR Pultruded Composites PIRASTM with C.M. PIR with Physical Property Method Units and Roving RovingSpecific Gravity D-792 — 1.73 1.93 Hardness D-2240-95 Shore D 84.0090.00 Glass Content D-2584-94 % 75.10 86.40 HDT @ 66 psi D-648-88 ° C.269.00 266.17 HDT @ 264 psi D-648-88 ° C. 280.12 252.48 CLTE D-696 10 ×e⁻⁶ 5.11 N/D ° C. Izod Parallel D-256-93a Ft-lbs/in 40.6 Sample splitIzod D-256-93a Ft-lbs/in 13.4 Sample split Perpendicular FlexuralModulus D-790-95A kg/cm² 116,475 271,730 (Parallel) Flexural ModulusD-790-95A kg/cm² 33323 37730 (Perpendicular) Strain @ Break D-790-95A %2.9 2.1 (Parallel) Strain @ Break D-790-95A % 4.9 1.0 (Perpendicular)Tensile Modulus D-638-95 kg/cm² >304459 458407 Tensile Strength D-638-95kg/cm² >3552 5823

[0156] In example 17, the motor oil is used as an internal mold releaseagent. The motor oil employed has the composition below: Material %Weight Base oil stock¹ 71.5-96.2 Metallic Detergent²  2-10 AshlessDispersant³ 1-9 Zinc Dithiophosphate 0.5-3.0 Antioxidant⁴ 0.1-2.0Friction Modifiers⁵ 0.1-3.0 Antifoam⁶ 2-15 ppm Pour Point Depression⁷0.1-1.5

EXAMPLE 18

[0157] The method of example 17 is repeated at 250 Index except thatreaction mixture is applied by hand onto the reinforcement glass fibersand then pulled through the curing die. The fibers are in the form of 60tows of a 450 weight roving and are used at a volume fraction of 65% ofthe composite. The curing die is 45.7 cm long and the cross sectionprofile is 0.25″×0.21″. The pull speed is about 30.5 cm/min. The front,middle and end zones of the curing die are at 125° C., 125° C. and 125°C. respectively. Under these conditions, 609.6 cm of pultruded compositeare formed over a period of 1200 seconds.

EXAMPLE 19

[0158] The procedure of example 18 is repeated except that Isocyanate Eis employed. Polyol Component Parts by Weight Polyol A 87.4 DPG 12.6Dabco T-45 0.38 Loxiol G71S 8.0 Motor Oil 8.0 116.38Isocyanate:Isocyanate E Index: 200

[0159] Under those conditions, 609.6 cm of pultruded composite areformed over a period of 1200 seconds.

EXAMPLE 20

[0160] The procedure of example 19 is repeated except that the index is400. Under these conditions, 609.6 cm of pultruded composite are formedover a period of 1200 seconds.

PULTRUSION OF POLYURETHANES

[0161] In accordance with a further aspect of the invention,polyurethanes useful in manufacture of fiber reinforced polyurethanematrix composites by RIM and pultrusion are produced from immiscible andmiscible polyurethane systems.

[0162] In pultrusion of the polyurethane systems employed in theinvention, the isocyanate and polyol components are supplied to a Cannon2-component RIM machine for metering of these components to a staticmixer. The minimum throughput of the RIM machine is about 4.5 gram/sec.The static mixer is equipped with 22 polypropylene elements and combinesthe components to provide a reaction mixture. The diameter of the mixeris 9.4 mm and its length is 185 mm. The pultrusion machine is thePulstar 2408 machine configured with the closed injection die and azoned curing die described above.

Immiscible Polyurethane Systems EXAMPLE 21

[0163] In this example, an immiscible polyurethane system is employed.The polyol component and the isocyanate are given below. The amounts ofthe materials in the polyol component are expressed in wt. percent basedon the total weight of the polyol component. Polyol Component AmountPolyol X 80.96 Glycerin 4.26 Dabco 33LV 3.49 Dabco T-12 0.32 Unitol DSR4.86 Loxiol G71S 5.11 Niax L-5440 0.43 Kemester 5721 0.57 Total 100.00Isocyanate Component:Isocyanate A Index: 105

[0164] Isocyanate A, at a temperature of 25° C. is added to the polyolcomponent at a temperature of 25° C. to produce a reaction mixture. Thereaction mixture is gently mixed by hand with a tongue depressor for 10seconds without imparting shear force. Upon addition of isocyanate tothe polyol, an immiscible reaction mixture is produced. As reaction ofthe isocyanate and polyol progresses, the reaction mixture becomesmiscible and transparent. As the reaction proceeds further, theviscosity of the reaction mixture increases as the reaction mixturebecomes translucent and then opaque at the gel point at 210 sec. at roomtemperature. This change in viscosity of the reaction mixture aids inwetting of glass fiber reinforcement.

Effect of Viscosity of Polyol

[0165] Table 8 shows the viscosity of the polyol component of example 21at various temperatures. As the temperature increases, the viscosity ofthe polyol component decreases. This behavior helps thorough mixing ofisocyanate with the polyol component to improve wetting of thereinforcement material. TABLE 8 Viscosity of the Polyol Component vs.Temperature Temperature of Polyol ° C. Viscosity(cps) 25 200 32 158 40105 45 95

Effect of Viscosity of Reaction Mixture on Gel Time

[0166] Table 9 shows the vicsocity and gel times of the reaction mixtureof example 21. TABLE 9 Gel Time of Reaction Mixture vs. TemperatureTemperature of Reaction Mixture ° C. Gel Time (Sec.) 25 47 32 39 40 3145 22

Effect of Catalyst Blend on Gel Time

[0167] Table 10 shows the effect of catalyst blend on gel time of thereaction mixture of example 21 at various temperatures. TABLE 10 Dabco33LV and Dabco T-12 catalyst (Parts by weight 1:0.1 ratio) Gel DabcoDabco (sec.)@ Gel (sec.)@ Gel(sec.)@ Gel(sec.)@ 33LV T-12 25° C. 35° C.60° C. 80° C. 0.000 0.000 440 254 101  38 0.082 0.008 345 250  ND* ND0.164 0.016 325 245 ND ND 0.246 0.024 275 235 ND ND 0.328 0.032 215 215ND ND 0.410 0.041 195 176 ND ND 0.492 0.049 175 150 55 28 0.574 0.057150 135 ND ND 0.656 0.065 125 115 ND ND 0.740 0.074 110 103 ND ND 0.8200.082 106 ND 35 15 1.220 0.122 103 ND 29 10 2.030 0.203  93  55 ND ND3.168 0.317  40  32  7  2

Effect of a Single Catalyst on Gel Time

[0168] The gel time of the polyurethane reaction mixture of example 21also can be controlled by varying the amount of Dabco 33 LV catalyst andthe temperature of the reaction mixture. This is illustrated in Table11. TABLE 11 Effect of Dabco 33 LV Catalyst on Gel Time at VariousTemperature Dabco 33 LV (g) Gel time (sec.)@25° C. Gel time (sec.)@40°C. 0.0 902 176 0.28 875 ND 0.55 620 113 0.82 340 ND 1.10 245  62 1.37170  48 2.73 64  24 4.10 40  15 5.47 33 ND 6.83 28  09

EXAMPLE 22

[0169] In another aspect of the invention, the polyurethane system belowis modified with varying amounts of Dabco T-45 catalyst. All amounts ofmaterials in the polyol component are expressed as percent by weightbased on the total weight of the polyol component. Polyol ComponentAmount Polyol X 82.6 Glycerine 4.35 Zinc Stearate 8.7 L-5440 4.35 Total:100

[0170] The weight percent amounts of Dabco T-45 based on the totalweight of the polyol component, and the effect of Dabco T-45 on the geltime of the system are shown in Table 12. TABLE 12 Effect of Dabco T-45on Gel Time Dabco T-45 (g) Gel time (sec.) @ 25° C. Gel time (sec.) @130° C. 0.0 did not cure did not cure 0.1 1800 160 0.2 710 130 0.3 380120 0.5 270 100 1.0 200 100 2.0 110 79 3.0 89 40

EXAMPLE 23

[0171] The procedure of example 22 is repeated except that a mixture ofDabco T-45 and BiCat 8 is added to the polyol component. The effect ofthis mixture of catalysts on gel time at various temperatures of thereaction mixture with and without milled glass in the reaction mixtureis shown in Table 13. TABLE 13 Effect of mixture of Dabco T-45 andBiCat-8 Catalysts (1:1 Ratio) on Gel Time at Various Temperatures* Gel @Gel @ Gel @ Gel @ Amount of 25° C. 25° C. 130° C. 130° C. Dabco T-45Without with 50% 0% milled 50% milled and BiCat 8 milled glass milledglass glass glass 0.1 (g) 410 sec 450 sec 140 sec 180 sec 0.2 45 150 30115

EXAMPLES 24-24AK

[0172] In this aspect of the invention, LC 5615 and UAX 1075 catalystsare used in combination with internal mold release agents in thepolyurethane system below. The amounts of the materials in the polyolcomponent are expressed as wt. % based on total weight of the polyolcomponent. Polyol Component Amount Polyol X 84.82 Glycerine 4.46 L-54400.45 IMR* 5.36 LC 5615 0.45 UAX 1075 4.46 Total 100.00

[0173] In these examples, varying amounts of LC 5615, UAX 1075, Munch7027/A, Munch 7016 and Munch 0669/1BB are added to the polyol component.The effect of these catalysts and mold release agents on gel time of thepolyurethane reaction mixture are given in Table 14: TABLE 14 Effect onGel Time Using Various IMRS at Various Temperature Component/ UAX MunchMunch Munch Ex. Temp. LC 5615 1075 7027/A 7016 0669/1BB Gel Time 24A 25C. 0.01 (g) 0.10 (g) 6 (g) — (g) — (g) 720 (sec) 24B 25 0.05 0.50 6 — —630 24C 25 0.10 1.00 6 — — 550 24D 25 0.15 1.50 6 — — 410 24E 25 0.202.00 6 — — 385 24F 25 0.40 4.00 6 — — 350 24G 25 0.50 5.00 6 — — 315 24H25 0.01 0.10 — 6 — 768 24I 25 0.05 0.50 — 6 — 635 24J 25 0.10 1.00 — 6 —620 24K 25 0.15 1.50 — 6 — 490 24L 25 0.20 2.00 — 6 — 445 24M 25 0.404.00 — 6 — 395 24N 25 0.50 5.00 — 6 — 340 24P 25 0.01 0.10 — — 6 786 24Q25 0.05 0.50 — — 6 750 24R 25 0.10 1.00 — — 6 615 24S 25 0.15 1.50 — — 6520 24T 25 0.20 2.00 — — 6 470 24U 25 0.40 4.00 — — 6 385 24V 25 0.505.00 — — 6 360 24W 140 0.01 0.10 6 — — 185 24X 140 0.05 0.50 6 — — 17424Y 140 0.10 1.00 6 — — 160 24Z 140 0.15 1.50 6 — — 140 24AA 140 0.202.00 6 — — 125 24AB 140 0.40 4.00 6 — — 120 24AC 140 0.50 5.00 6 — — 9824AD 140 0.01 0.10 — 6 — 210 24AE 140 0.05 0.50 — 6 — 196 24AF 140 0.101.00 — 6 — 160 24AG 140 0.15 1.50 — 6 — 140 24AH 140 0.20 2.00 — 6 — 12524AI 140 0.40 4.00 — 6 — 105 24AJ 140 0.50 5.00 — 6 — 95 24AK 140 0.010.10 — — 6 216 24AL 140 0.05 0.50 — — 6 200 24AM 140 0.10 1.00 — — 6 18524AN 140 0.15 1.50 — — 6 160 24AP 140 0.20 2.00 — — 6 130 24AQ 140 0.404.00 — — 6 115 24AR 140 0.50 5.00 — — 6 954

EXAMPLES 25A-25AS

[0174] The process of example 24 is repeated except that the amounts ofMunch and Loxiol are held constant and the amounts of LC 5615 and UAX1075 are varied. All amounts below are expressed in weight percent basedon total weight of the polyol component. Component Amount Polyol X 80.50Glycerine 4.10 L 5440 0.40 Loxiol 5.15 Munch IMR* 5.15 LC 5615 0.40 UAX1075 4.30 Total: 100.00

[0175] The effects on gel time of these internal mold release agents areshown in Table 15. TABLE 15 Effect on Gel Time Using Various IMRS atVarious Temperature Munch Munch Munch Component/ 7027/A: 7016: 0669/1BB:Ex. Temp LC 5615 UAX 1075 Loxiol Loxiol Loxiol Gel Time 25A 25 C.0.01(g) 0.1 (g) 6:6 (g) — (g) — (g) 740 (sec) 25B 25 0.05 0.5 6:6 — —650 25C 25 0.10 1.0 6:6 — — 580 25D 25 0.15 1.5 6:6 — — 430 25E 25 0.202.0 6:6 — — 398 25F 25 0.40 4.0 6:6 — — 368 25G 25 0.50 5.0 6:6 — — 31525H 25 0.01 0.1 — 6:6 — 795 25I 25 0.05 0.5 — 6:6 — 656 25J 25 0.10 1.0— 6:6 — 605 25K 25 0.15 1.5 — 6:6 — 510 25L 25 0.20 2.0 — 6:6 — 465 25M25 0.40 4.0 — 6:6 — 418 25N 25 0.50 5.0 — 6:6 — 368 25P 25 0.01 0.1 — —6:6 810 25Q 25 0.05 0.5 — — 6:6 750 25R 25 0.10 1.0 — — 6:6 665 25S 250.15 1.5 — — 6:6 586 25T 25 0.20 2.0 — — 6:6 496 25U 25 0.40 4.0 — — 6:6410 25V 25 0.50 5.0 — — 6:6 385 25W 140 0.01 0.1 6:6 — — 199 25X 1400.05 0.5 6:6 — — 180 25Y 140 0.10 1.0 6:6 — — 172 25Z 140 0.15 1.5 6:6 —— 156 25AA 140 0.20 2.0 6:6 — — 135 25AB 140 0.40 4.0 6:6 — — 128 25AC140 0.50 5.0 6:6 — — 110 25AD 140 0.01 0.1 — 6:6 — 225 25AE 140 0.05 0.5— 6:6 — 210 25AF 140 0.10 1.0 — 6:6 — 186 25AG 140 0.15 1.5 — 6:6 — 15525AH 140 0.20 2.0 — 6:6 — 130 25AJ 140 0.40 4.0 — 6:6 — 115 25AK 1400.50 5.0 — 6:6 — 102 25AL 140 0.01 0.1 — — 6:6 229 25AM 140 0.05 0.5 — —6:6 210 25AN 140 0.10 1.0 — — 6:6 196 25AP 140 0.15 1.5 — — 6:6 181 25AQ140 0.20 2.0 — — 6:6 162 25AR 140 0.40 4.0 — — 6:6 140 25AS 140 0.50 5.0— — 6:6 124

[0176] Preferably, about 0.40 gram of LC 5615 and about 4.0 gram UAX1075 are used per 100 gram of polyol component. More preferably, about0.35 gram of LC 5615 and about 1.5 gram UAX 1075 are used per 100 gramof polyol component.

Polyurethane Systems with Internal Mold Release Agents EXAMPLE 26

[0177] In this aspect of the invention, LC 5615 and UAX 1075 catalystsare used in combination with internal mold release agents. The amountsof the materials in the polyol component are expressed as weight percentbased on the total weight of the polyol component. Polyol ComponentAmount Polyol X 77.18 UAX 1075 1.05 LC-5615 1.46 DPG 16.25 Munch 7027/A4.06 Total 100.00

[0178] The polyurethane polymer produced from this polyurethane systemhardens at 6.5 min. at room temperature and cures in less than oneminute at 300 F on a hot plate.

EXAMPLE 27

[0179] In this example, LC 5615 and UAX 1075 catalysts are used incombination with internal mold release agents in the polyurethane systembelow. The amounts of the components in the polyol component areexpressed as weight percent based on the total weight of the polyolcomponent. Polyol Component Amount PPG 425 60.60 UAX 1075 0.98 LC-56151.15 DPG 31.90 Munch 7027/A 4.88 L-5440 0.49 Total 100.00

[0180] The polyurethane polymer produced from this polyurethane systemhardens at 5.0 min. at room temperature and cures in 30 seconds at 300 Fon a hot plate. The reaction mixture produced from this polyurethanesystem is completely miscible visually after 20-25 seconds on additionof the isocyanate to the polyol component and mixing by hand with atongue depressor with low shear force.

EXAMPLE 28

[0181] The procedure of example 27 is followed except that LHT 240 issubstituted for PPG 425. The polyurethane polymer produced from thispolyurethane system hardens at six min. at room temperature cures in 30seconds at 300 F on a hot plate. The reaction mixture produced from thispolyurethane system is completely miscible visually after 20-25 secondson addition of the isocyanate to the polyol component and mixing by handwith a tongue depressor with low shear force.

Polyurethane Systems with Internal Mold Release Agents and CatalystsEXAMPLE 29

[0182] In this example, LC 5615 and UAX 1075 catalysts are used incombination with internal mold release agents in the polyurethane systembelow. The amounts of the materials in the polyol component areexpressed as weight percent based on the total weight of the polyolcomponent. Polyol Component Amount Polyol X 15.50 Polyol Y 15.50 LHT 24046.50 UAX 1075 1.50 LC-5615 1.50 DPG 18.50 Munch 7027/A 0.65 L-5440 0.35Total 100.00

[0183] The polyurethane polymer produced from this polyurethane systemhardens at six min. at room temperature and cures in 20 seconds at 300 Fon a hot plate. The reaction mixture produced from this polyurethanesystem is completely miscible visually after 50 seconds on addition ofthe isocyanate to the polyol component and mixing by hand with a tonguedepressor with low shear force.

EXAMPLE 30

[0184] In this example, a two component immiscible polyurethane systemis pultruded. The polyol component and the isocyanate are given below.The amounts of the materials employed in the polyol component areexpressed in wt. percent based on the total weight of the polyolcomponent. Polyol Component Amount Polyol X 68.98 Glycerin 3.63 Dabco DC1027 0.36 Fomrez UL-29 0.04 Loxiol G71S 4.36 Niax L-5440 0.36 Kemester5721 0.49 Zinc Stearate 7.26 Kaolin (Clay) 14.52 Total 100.00

[0185] In this example, the polyol component at a temperature of 25° C.and isocyanate at a temperature of 25° C. are reacted in the closedinjection die described above in the presence of glass fiberreinforcement and pultruded to produce glass fiber reinforcedpolyurethane composites.

EXAMPLE 30A

[0186] The polyol component employed in example 30 having a hydroxylvalue of 471, water content of 0.28%, and a viscosity of 2759 cps, andIsocyanate A are supplied to a static mixer at a weight ratio ofisocyanate to polyol component of 1.27 to produce a reaction mixture.The time for the initiation of reaction mixture to form a gel and tocure to hardness at room temperature and on a hot plate heated to 200°C. is shown in Table 16. TABLE 16 Initiation of Reaction to FormHardening Gel¹ Gelling Stage Stage Temperature 7.1-7.15 Min. 8.25-8.3Min. 9.1-9.2 Min. 25° C. 2.1-2.15 3.25-3.3 4.1-4.2 200 on a Hot Plate

[0187] The reaction mixture produced in the static mixture is injectedat 3.06 atm. into the injection die shown in U.S. Pat. No. 5,783,013while glass fiber reinforcement is supplied to the die. The glass fiberreinforcement is supplied to the die as a set of top, middle and bottom366 Type 30 rovings from Owens Corning Fiberglass Co. to achieve 40-45%by weight of glass reinforcement in the pultruded product. The top andbottom rovings include four layers of 16 rows of tows in each roving.Each tow includes about 4000 filaments which are sized with aminosilane.The middle layer includes four layers of continuous strand glass mat atan areal density of about 0.78 gm/cm 2 of M8643 glass fibers from OwensComing Fiberglass Co, each of which are separated by a single layer of16 rows of tows. Each tow includes about 4000 filaments which are sizedwith aminosilane.

[0188] Using a pull force of 3558-5338 newton, and a pull speed of 35.56cm per minute, the reaction mixture with glass fiber reinforcement ispultruded through the injection die at 25 C to the curing die. Thefront, middle and end portions of the curing die are at the temperaturesbelow: Front Middle End Upper Mold of the Die 220° C. 215° C. 217° C.Lower Mold of the Die 219° C. 216° C. 218° C.

[0189] Under these conditions, 355.6 cm of pultruded glass fiberreinforced polyurethane composite is pultruded during a period of 900seconds.

EXAMPLE 31

[0190] The procedure of example 30A is repeated except that the front,middle and end portions of the injection die are heated to thetemperatures below: Front Middle End Upper Mold of the Die 240° C. 246°C. 220° C. Lower Mold of the Die 240° C. 246° C. 220° C.

[0191] Under these conditions, 355.6 cm of pultruded glass fiberreinforced polyurethane composite is pultruded during a period of 1200seconds.

EXAMPLE 32

[0192] The procedure of example 30A is repeated except that the amountof glass fiber reinforcement is increased to 45-50% by weight of thepultruded product. Under these conditions, 533.4 cm of pultruded glassfiber reinforced polyurethane composite is pultruded during a period of1800 seconds.

EXAMPLE 33

[0193] The procedure of example 32 is repeated except that the amount ofglass fiber is increased to 50-55% by weight of the pultruded product.Under these conditions, 355.6 cm of pultruded glass fiber reinforcedpolyurethane composite is pultruded during a period of 1800 seconds.

EXAMPLE 34

[0194] The procedure of Example 33 is repeated except that the pullforce is 4448-6227 newton, the pull speed is 40.6 cm per minute, and thefront, middle and end portions of the die are heated to the temperaturesbelow: Front Middle End Upper Mold of the Die 260° C. 260° C. 220° C.Lower Mold of the Die 260° C. 260° C. 220° C.

[0195] Under these conditions, 533.4 cm of pultruded glass fiberreinforced polyurethane composite is pultruded during a period of 840seconds.

EXAMPLE 35

[0196] The procedure of example 34 is repeated except that the pullspeed is 61 cm per minute. Under these conditions, 533.4 cm of pultrudedglass fiber reinforced polyurethane composite is pultruded during aperiod of 720 seconds.

EXAMPLE 36

[0197] The procedure of example 35 is repeated except that the pullspeed is 76.2 cm per minute, and the amount of glass fiber reinforcementis increased to 60-65% by weight of the pultruded product. Under theseconditions, 22.86 meters of pultruded glass fiber reinforcedpolyurethane composite is pultruded during a period of 1800 seconds.

[0198] Table 17 shows the properties of the glass fiber reinforcedpolyurethane composite pultruded at pull speed of 76.2 cm per minute.TABLE 17 Parallel to Perpendicular ASTM Fiber to Fiber Property MethodUnits Alignment Alignment Amount of glass fiber — % 70 70 by weightSpecific Gravity D 792 — 1.43 1.44 Flexural Modulus D 790 Psi 3,460,000330,000 Stress @ Break D 790 Psi 42,000 6,870 Strain @ Break D 790 % 1.64 Izod Impact @ D 256 ft lbs/in 33.54 6.64 73 ^(C)F Notched TensileModulus D 638 Psi 3,500,000 543,000 Tensile Stress @ D 638 Psi 48,0008,730 Break Tensile Strain @ D 638 % 0* 2.24 Break CLTE D 696 C 3.6 13.8HDT @ 264 Psi D 648 C 249 175 HDT @ 66 Psi D 648 C 260 222 WaterAbsorption D 570 % 2.11 1.43

[0199] The invention provides numerous advantages. For example,increased pull speeds through control of the reaction rate of thepolyisocyanurate reaction mixture in both the injection die and thecuring die. The invention, through use of a static mixer, also enablesincreased exposure times of the reaction mixture to the glass fiberreinforcement in the injection die to more thoroughly wet the glassfiber reinforcement. In addition, the polyisocyanurates of the inventionprovide fast reactions and enable high production rates, but produceproducts which have flexural strengths comparable to polyester and muchgreater flexibility than polyester.

[0200] The polyisocyanurate systems of the invention advantageously canbe tailored to achieve a wide range of initiation times to facilitatepultrusion of polyisocyanurates and fiber reinforced polyisocyanuratematrix composites over a broad range of pultrusion line speeds.

[0201] The polyisocyanurate systems of the invention advantageously haveextended initiation times of about 5 minutes to about 30 minutes at roomtemperature, and can be snap cured. These characteristics aid wetting ofglass fiber reinforcement and production of high strength, uniform fiberreinforced polyisocyanurate matrix composites.

What is claimed:
 1. A reaction system for the preparation of a fiberreinforced composite in a pultrusion process, the reaction systemcomprising: a) a liquid reaction mixture formed by combining a polyolcomponent and a polyisocyanate component; and b) a continuous fiberreinforcing material, wherein the liquid reaction mixture initiallycontains both free isocyanate groups and free alcoholic —OH groups, andgels between 340 and 768 seconds at 25° C. and between 95 and 210seconds at 140° C.
 2. The reaction system according to claim 1, whereinthe reaction mixture contains release agent.
 3. The reaction systemaccording to claim 1, wherein the reaction mixture contains one or morecatalysts suitable for promoting at least one reaction selected from thegroup consisting of the reaction of isocyanate groups with alcoholgroups to form urethane bonds, and the trimerization of isocyanategroups to form isocyanurate groups.
 4. The reaction system according toclaim 1, wherein the Index of the reaction mixture is from 200 to 1000and the reaction mixture contains at least one catalyst for thetrimerization of isocyanate groups.
 5. The reaction system according toclaim 1, wherein the Index of the reaction mixture is less than
 200. 6.The reaction system according to claim 1, wherein the reaction mixtureis devoid of amines.
 7. The reaction system according to claim 6,wherein the reaction mixture contains metal carboxylate release agent.8. The reaction system according to claim 7, wherein the metalcarboxylate release agent is selected from the group consisting of zincstearate, calcium stearate, and mixtures of thereof.
 9. The reactionsystem according to claim 1, wherein the reaction mixture containsphosphate release agent.
 10. The reaction system according to claim 1,wherein the reaction mixture contains aromatic polyester polyol.
 11. Thereaction system according to claim 1, wherein the reaction mixturecomprises isocyanate terminated prepolymer.
 12. A reaction systemsuitable for the preparation of a fiber reinforced composite by means ofa pultrusion process comprising: a) a liquid reaction mixture formed bycombining a polyol component and a polyisocyanate component; and b) acontinuous fiber reinforcing material, wherein the liquid reactionmixture initially contains both free isocyanate groups and freealcoholic -OH groups, has a gel time in the range of 84 to 600 secondswhen maintained at 23° C., and cures within 1 minute when heated to acure temperature in the range of 120 to 140° C.
 13. The reaction systemaccording to claim 12, wherein the reaction mixture comprises at leastone member selected from the group consisting of fatty ester releaseagent, phosphate release agent, wax release agent, fatty amide releaseagent, hydrocarbon release agent having from 10 to 19 carbon atoms,polyester polyol, metal carboxylate release agent, and mixtures thereof.14. The reaction system according to claim 12, wherein thepolyisocyanate component comprises isocyanate terminated prepolymer. 15.The reaction system according to claim 12, wherein the polyisocyanatecomponent is a mixture of 2,4′-MDI, 4,4′-MDI, and pMDI, having about19.5% by weight 2,4′-MDI, 60.9% by weight 4,4′-MDI, and 19.6% by weightpMDI, and having an NCO value of 32.5.
 16. The reaction system accordingto claim 12, wherein the polyisocyanate component comprises uretoniminemodified MDI.
 17. The reaction system according to claim 12, wherein thepolyisocyanate component comprises polymeric MDI.
 18. The reactionsystem according to claim 12, wherein the reaction mixture containsalkali carboxylate catalyst.
 19. The reaction system according to claim18, wherein the alkali carboxylate catalyst comprises a potassiumcarboxylate.
 20. The reaction system according to claim 12, wherein thereaction mixture contains a blocked amine catalyst.
 21. The reactionsystem according to claim 12, wherein the reaction mixture contains atertiary amine catalyst.